Diazo-salt preparation



Patented May 13, 1930 UNITED: s r-Ares PATENT oar-lea FERDINAND KELLER AND KARL SGHNI'IZSPAHN, OFFENBACH+OH-THEHAIN, GE- ANILINE WORKS, INC., 01' NEW YORK, H. Y., A.

my, assronons ro GENERAL rona'rron or DELAWARE nmzo-sanr :ennrmrron Io Drawing. Application filed December 8, 1925, Serial No. 74,161, and in Germany December 87, '18.

This invention relates to new diazo-salt preparations, which consist of mixtures of aromatic diazocompounds in a solid form,-

with metal salts of arylsulfonic acids. 5 In. the'diazo salt preparations heretofore appearin facilitating the drying and lessening the explosive danger, only inorganic diluting materials such as sodium sulfate, burnt alum or especially valuable characteristics in that in the case of greatly diminished tendency to explosion, not only is-the stability of such diazopreparations greater than that of the corresponding preparations with inorganic diluting materials, but also the important property of solubility of the preparations in question is favorably influenced in a wholly unexpected way by the choice of suitable aryl-- sulfonates. By the admixture of suitable arylsulfonates, it is possible to convert into commercially useful preparations many diazosalts which would be useful theoretically in view of their stability and their coloring powers, but the use of which is impossible, due to theirbeing difiicultly soluble, as'suitable arylsulfonates are used such as form easily' soluble salts and not difiicultly soluble salts with the diazocompounds in question. Especially suitable are the metal salts of benzol sulfonic acids and benzol disulfonic acids or metal salts of benzyl-and-1.2.3L4-tetrahydronaphthalene-sulfonic acids and metal salts of di-and-poly-sulfonic acids of the naphthalene series, such as alkali metal salts -of naphthalene1.6, 1.7and 2.7--.disulfonic acids aswell as alkali metal salts of naphthalene trisulfonic-and-tetrasulfonic acids. The arylsulfonic acid metal salts may be added to .the separated and dried diazocompounds or they may be added to the precipitated and filtered, but still moist diazocompounds before drying the diazocompounds, whereby the danger incident to the drying may be greatly diminished in such a manner.

on the market, there have been used as diluting materials for the purpose oi Besides the arylsulfonic acid metal salts,

Ewample .2

- 46 parts of d p-chlorbenzolsultonic acid salt of diazotize p-nitroaniline, which is obtained by treating a suficiently concentrated mineral acid diazosolution with p-chlorbenzolsulfonic acid salt, are ound with 49 parts of commercial sodium sa t of 1.6-na hthalene 3(,Eiisulfonic acid and 5 parts ofalummum sulate;

An excellently soluble and stable product is obtained.

' Ewample 3 46 parts of filtered, moist chlorzinc double salt of diazotized 4-chlor-2-nitro-1-aniline of 38% chlornitroaniline content obtained as described above, are mixed with 63 parts of a mixture of sodium salts of naphthalene triand-tetra-sulfonic acids obtained by sulfonating 1 molecule of naphthalene with 4 molecules of sulfuric acid anhydride, and then dried at C. The drying operation proceeds without danger of explosion and yields a very stable product.

Emampl 4 82 parts of dry 1.5-naphthalene disulfonic acid diazo-m-nitroaniline of a nitroaniline content corresponding to 34%, prepared by reacting the diazosolution with the sodium salt of 1.5-naphthalene disulfonic acid, are

mixed with 98 parts of dry sodium salt of parts of sodium benzolsulfonic acid and 20 salt of tetralinsulfonic acid. v A good soluble product is obtained.

of 72% content are mixed with mixture of an aromatic prepared chalk an Eat-ample 5 37 parts of acid 1.5-naphthalene disulfonic' acid diazochlortoluidine (CH NH Cl= 1:2:4), prepared by reactin the diazosolution with free 1.5-naphtha ene disulfonic acids, are intimatel ground with 5 parts of 28 parts of commercial sodium salt of 1.6-naphthalenedisulfonic acid.

Similar products are obtained from the isomeric diazochlortoluidins.

Example 6' 103 arts of chlorzincdoublesalt of tetrazodianisidin of 49.3% dianisidin content are ground with 142 parts of sodium salt of 2.7 naphthalene disulfonic acid and 5 parts of, crystallized copper sulfate.

Ewample 7 280 parts of filtered wet diazosulfanilic acid 720 parts of sodium salt of 1.5-naphthalenedisulfonic C. The drying of the arylsulfo-' nate is characterized by the greatest danger of explosion, follows without any difiiculty. The expression astabilized diazo salt as. used in t e following claims is intended to comprise the heavy metal double salts of the aromatic diazo salts as well as the. salts formed or prepared by reacting a diazo solution with an aromatic sulfonic acid.

We claim: i

1. A diazo-salt preparation, comprising a diazo compound in a solid form with a soluble metal salt of an arylsulfonic acid.

2. A diazo-salt preparation, comprising a,

-m1xture of an aromatic diazo compound in a sohd form with a soluble metal salt of a naphthalene sulfonic acid which contains a plurality of sulfonic acid groups.

3. A diazo-salt preparation, comprising a 'mixture of an aromatic diazo salt in a solid .form, with a soluble metal salt of a naphthalene sulfonic acid which contains a plurality of sulfonic acid oups.

4. A diazo s t preparation comprising a mixture of a diazo salt in a solid form made from an aromatic amine having the general formula X -R- NH whereinR stands for an algl nucleus, 11. stands for the numeral 1 or 2, an X stands for sulfo, halogen, nitro, alkjyl l p v or alkoxy with a soluble metal salt of a na halene sulfonic acid which contains a plurality of sulfonic acid groups.

'5. A diazo salt preparation comprising a mixture of a dia'zo salt in a solidform made frame nitrated diazo compound of the benzeneseries-in which one hydrogen atom'may be"'"substituted by chlorine with a soluble metal salt of a naphthalenedisulfonic acid.

,6. A diazo-salt ing a mixture of a heavy metal double sa preparation comprising'a fonicacid.

8. A solid diazo-salt preparation comprising a stabilized aromatic diazo salt and a soluble metal salt of an arylsulfonic acid.

9. A solid diazo-salt preparation comprisin a stabilized aromatic diazo salt and an alkali metalsalt of an arylsulfonic acid.

10. A solid diazo-salt preparation comprising a stabilized aromatic diazo salt and'a soluble metal salt of a naphthalene sul honic acid which contains a plurality of sulfonic acid groups. I i

11. A solid diazo salt reparation com ris ing a mixture of a stabilized aromatic salt made from an aromatic amine having the general 'formula vX,,-RNH,- stands for an aryl nucleus, n 'stands for the numerald or 2, and X stands'for sulfo, halogen, nitro, alkyl or alkoxy and a soluble metal salt of a naphthalene sulfonic acid which contains a plurality of s'ulfonic-acid oups.

wherein R 12. A solid diazo salt reparation com ris- V inga mixture of a stabilized aromatic 'azo salt made from a nitrated diazo compound of the benzene series in which one hydrogen atom may be substitut d by chlorine, and a soluble metal salt of a n phthalene disulfonic acid.

13. A solid diazo-salt preparation compris an aromatic diazo salt and a soluble metal salt of an arylsulfonic acid.

14. A solid diazo-salt preparation com ris ing a mixture of a heavy metal double a t of an aromatic diazo salt and an alkali metal salt of an arylsulfonic acid.

15. A solid diazo-salt preparation comprising a mixture of a heavy metal double sa t of an aromatic diazo salt and a soluble metal salt of a na hthalene sulfonic acid which contains a plura ity of sulfonic acid groups.

16. A solid diazo-salt preparation com rising a mixture of a heavy metal double sa t of an aromatic diazo salt and an alkali metal salt of a naphthalene sulfonic acid which con? tains a plurality of sulfonic acid oups.

17. A solid diazo salt preparation'com rising a mixture of a heavy metal double sa t of an aromatic diazo salt made from an aromatic amine having the general formula X --R- NH wherein R stands for an aryl nucleus, 1: stands for the numeral 1 or 2 and X stands for sulfo, halogen, nitro, a or alko o and a soluble metal salt of anaphthalene ionic acid which contains a plurality of sulfonic acid groups.

4 1s. a solid diazo salt a aaaa am I ing a mixture of a heavy metaldouble 4 t of a nitrated diazo salt of the benzene series in which one hydrogen atom may be substituted by chlorine and a soluble metal salt of a naphthalene disulfonic acid.

In testimony whereof, we aflix our signatures.

DR. FERDINAND KELLER. KARL SCHNITZSPAHN. 

